Low melting crystallizing enamel for low emissivity coated glass substrate

Abstract

Described is a composition tailored in particular for automotive and flat glass applications as a glaze and / or enamel composition. Moreover, the present invention relates to a method of applying the composition on a Low-e coated side of a glass surface, in particular in the field of laminated automotive windshields, sunroofs, backlights produced via press bending process as well as architectural glass. Notably, composition according to the present invention facilitates Low-e coating dissolution and direct fusion to the glass substrate while preserving essential optical properties, and adhesion-meeting industry standards.

Description

[0001] Low melting crystallizing enamel for low emissivity coated glass substrate Description

[0002] The present invention relates to a composition tailored in particular for automotive and flat glass applications as a glaze and / or enamel composition. Moreover, the present invention relates to a method of applying the composition on a Low-e coated side of a glass surface, in particular in the field of laminated automotive windshields, sunroofs, backlights produced via press bending process as well as architectural glass. Notably, composition according to the present invention facilitates Low-e coating dissolution and direct fusion to the glass substrate while preserving essential optical properties, and adhesion-meeting industry standards.

[0003] Low-Emissivity (Low-E) coatings are thin, transparent layers applied to glass surfaces to reduce heat transfer and improve energy efficiency. These coatings are designed to reflect infrared (IR) radiation while allowing visible light to passthrough, helping to regulate temperature by minimizing heat loss in cold weather and reducing heat gain in hot weather.

[0004] Despite reflecting infrared heat, Low-E coatings are designed to allow visible light to pass through, ensuring that the natural brightness of the outdoors is not compromised. This makes Low-E glass energy-efficient while still being transparent and visually clear.

[0005] There are two main types of Low-E coatings, typically classified based on how they are applied and their functionality:

[0006] Soft Coat (High-Performance Low-E) coatings are made by depositing multiple layers of silver or other metals onto the glass using a vacuum deposition process. Soft coats are typically applied to the inside surfaces of the glass in insulating glass units (IGUs) (i.e., double or triple glazing). These coatings are more effective at reflecting infrared radiation, thus offering better insulation, but they are more vulnerable to damage and must be protected by placing them between layers of glass.

[0007] Hard Coat (Durable Low-E) coatings are made by applying a thin oxide layer to the glass during manufacturing, often as part of the glass itself. These coatings are more durable and scratchresistant compared to soft coats but are slightly less effective in reflecting infrared radiation. Hard coats are often used in single-glazed windows or as part of laminated glass.

[0008] Benefits of Low-E Coatings are the reduction of heating and cooling costs by improving the thermal performance of windows. In the winter, they minimize heat loss, and in the summer, they help keep the interior cool by reducing heat from outside. Low-E glass blocks a significant amount of ultraviolet (UV) light, which helps to prevent fading furniture, curtains, carpets, and other interior furnishings. By minimizing the transfer of heat, Low-E windows help maintain a consistent indoor temperature, improving comfort for building occupants. Finally, insulating glass units with Low-E coatings may offer some reduction in noise transmission from outside, although this is primarily achieved by increasing the number of glass layers or the thickness of the air space between them. That said, low-Emissivity (Low-E) coatings on glass play a crucial role in both automotive and architectural applications by enhancing energy efficiency and providing the various protective benefits mentioned above.

[0009] The majority of Low-E coatings are stack of few micrometers thin multilayer typically composed of silver protected with oxide / non-oxide protecting multi layers such as SnC>2, ZnAIOx, SiOx, SiaN4, SiOxNy, Nb2C>5, TiOx, ZnOx / AIOx, NiCrOx, ZnSnOx, indium-tin oxide (ITO), creating a smooth and non-porous surface. In certain applications, such as in the automotive glass industry, it may be necessary to decorate or cover portions of a glass substrate with enamel. For example, an obscuration enamel might be applied around the edges of the substrate to protect an underlying adhesive from UV damage. However, standard commercially available enamels are not suitable for use on glass substrates coated with Low-E coatings because they cannot completely etch through multilayer coatings. This limitation can lead to issues such as discoloration, poor adhesion, delamination, and loss of coating functionality.

[0010] To address this, the coating must first be removed chemically or mechanically using abrasive wheels or laser beams from the area where the enamel will be applied, allowing the enamel to fuse directly with the bare glass. This additional process is costly and can introduce quality defects, mechanical damage, create unwanted flaws, and reduce the mechanical properties of the final glass substrate.

[0011] To avoid the edge deletion process, different approaches were practiced.

[0012] One of these approaches is a two-step process disclosed in WO 2019 / 016639 A. In the first step, a provisional corrosive enamel in the form of a paste which contains inter alia P2O5-Na2O is applied to the desired area. The glass substrate is then fired at a temperature of 500 to 700 °C, where the provisional enamel digests the Low-e coating. After heating, the glass substrate is washed with water or a similar solution to remove excess material from the glass and then provided with a final enamel. However, this approach may not be suitable for most Low-e coating systems and has the disadvantage of introducing an extra step, as well as additional energy and cost.

[0013] WO 2021 / 023965 A provides another approach by using an enamel comprising 10 to 40 mol% ZnO, 20 to 40 mol% B2O3, 25 to 65 mol% Bi2O3, TeO2, or PbO, or mixtures thereof, and up to 15 mol% Al2O3. It is disclosed that this enamel is a suitable one-step solution to etch multilayer coated including low-E coated glass substrates and can be used to decorate or cover the coated glass without causing defects such as discoloration, lack of adhesion, delamination, and loss of coating functionality. However, in automotive glass manufacturing, the press bending process requires specific anti-stick properties to ensure smooth operation and high-quality end products. These requirements are not fulfilled by the teaching of WO 2021 / 023965 A. Such compositions are known as low melting and mainly used in sealing application for flat glass. In earlier studies it has been found that such glass compositions can dissolve low-E coating systems. But after firing these compositions form high glossy surfaces and cannot used for bending. Even these compositions need high temperatures for the dissolving of the low-E coating which cannot be applied in the production of laminated glasses for automotive application. An alternative approach is disclosed in WO 2014 / 133929 A, where the ceramic frit chemically attacks and dissolves the Low-E coating at elevated temperatures. However, this solution does also not address the anti-stick properties required for press bending of automotive glass.

[0014] Another approach is disclosed in WO 2021 / 122856 A and WO 2021 / 165342 A, in which an anti-stick paint is first applied and pre-fired. Thereafter, a multilayer coating on the glazing and on at least a part of the fired enamel coating on the glazing is deposited to form a coated glass sheet.

[0015] A further prior art reference in the underlying technical field is US 10,745,317 which discloses an enamel composition for sealing of low-e coated float glass without damaging low-e coating structure. The glass frit of the enamel were added with 0.5-20 wt% iron oxide and / or manganese oxide.

[0016] WO 2021 / 023965 A discloses in examples 1 and 2 enamel compositions for coating low-e coated float glass. The enamel comprises a glass frit and black pigments. Black pigments implicitly comprise iron and / or manganese.

[0017] WO 2021 / 107707 A discloses an enamel composition for coating low-e coated float glass. The enamel comprises a glass frit and black pigments. Black pigments comprise iron and / or manganese.

[0018] US 5252 521 A discloses enamel compositions comprising a glass frit and a Mn-containing pigment.

[0019] As low-E coating dissolving enamels primarily rely on low melting glass compositions, achieving the desired anti-stick properties at the end of the firing process proves challenging. Additionally, the introduction of common crystallizing agents, well-known to experts in the field, may adversely affect the efficiency of the enamel's coating removal function. However, WO 2022 / 153001 A discloses refractory particles, ranging in diameter from 20 to 80 microns, being applied together with the enamel. This creates a sufficiently large gap between the pressing tool and the glass substrate. In other words, this ceramic color paste has a mold releasability and can be used in a production method where two sheets of glass are bent and formed simultaneously. However, using coarse refractory particles can negatively affect production efficiency due to the risk of obstructing the sieve mesh with such coarse particles.

[0020] Therefore, there is still a need for a more efficient one-step technique to apply non-adhering enamel onto low-E coated glass substrates, ensuring robust adhesion and preventing undesired color alterations. Additionally, it should meet the anti-stick criteria required for shaping automotive glass through pressing.

[0021] The present invention solves these problems by meticulously selecting a suitable composition of a glass composition and a ceramic enamel to ensure complete dissolution of commercially available low-E coating systems applied by a PVD process. The present formulation dissolves in particular soft coatings. As a result, the enamel fuses directly to the glass surface (bare glass), providing thereby the proper anti-stick properties necessary for press bending without addition of coarse refractory particles in the enamel.

[0022] The present invention provides in a first aspect a glass composition, comprising, based on the total weight of the composition, bismuth ions in an amount of 30 to 80 wt.%, calculated as Bi2C>3, zinc ions in an amount of 3 to 30 wt.%, calculated as ZnO, boron ions in an amount of 0,1 to 20 wt.%, calculated as B2O3, and alkali ions such as sodium ions, potassium ions and lithium ions in an amount of 0,1 to 10 wt.%, calculated as Na2O, K2O, and Li2O. Such alkali oxides are preferred to reduce the melting temperatures (softening and liquidus temperature) of the claimed composition as shown in Figure 3.

[0023] The claimed composition is characterized in that the weight ratio between bismuth ions and zinc ions, calculated as Bi2O3and ZnO, is 3 to 14.

[0024] It has been found surprisingly that such a glass composition, together with further components, are suitable for facilitating low-e coating dissolution and direct fusion to the glass substrate while preserving essential optical properties, and adhesion-meeting industry standards.

[0025] Nowadays standard black anti-stick enamels consist mainly of one or more glass fluxes containing Bi2O3, ZnO, B2O3, R2O, RO2and SiO2, mainly Cu-Cr spinels and / or Mn-Cu-Cr spinels and bismuth or zinc silicate. The bismuth or zinc silicate is a seed material so that the glass enamel partially crystallizes during firing and prevents bonding between the two glass panes or between the glass pane and the bending tools during bending. However, these enamels cannot dissolve low-E coatings during firing. In the best-case scenario, these enamels are compatible with the low-E coating without causing any defects. These enamels adhere directly to the low-E coating and not fuse directly to the glass substrate.

[0026] The present invention now provides an alternative for such anti-stick enamels which can dissolve the low-E coating and forms a matt surface suitable for the bending process even at low temperatures.

[0027] In one aspect of the present invention, the weight ratio between bismuth ions and zinc ions, calculated as Bi2O3and ZnO, is 5 to 14.

[0028] In a further aspect of the present invention, the weight ratio between bismuth ions and zinc ions, calculated as Bi2O3and ZnO, is 7 to 14.

[0029] In the following, the composition of the composition according to the present invention is further described.

[0030] In one aspect, the composition according to the present invention comprises bismuth ions in an amount of 40 to 79 wt%, more preferably 60 to 78 wt%, based on the total weight of the composition, calculated as Bi2O3. In a further aspect, the composition according to the present invention comprises 3 to 20 wt%, more preferably 5 to 18 wt%, zinc ions, based on the total weight of the composition, calculated as ZnO.

[0031] In a further aspect, the composition according to the present invention comprises 0,1 to 18 wt%, more preferably 0,1 to 15 wt%, boron ions, based on the total weight of the composition, calculated as B2O3.

[0032] In a further aspect, the composition according to the present invention comprises 0,1 to 8 wt.%, more preferably 0,1 to 7 wt.%, based on the total weight of the composition alkali ions such as sodium ions, potassium ions and lithium ions, calculated as Na2O, K2O, and Li2O.

[0033] In a further aspect, the composition according to the present invention comprises silicon ions in an amount of 0 to 5 wt.%, preferably 0 to 3 wt.%, more preferably 0 to 2 wt.%, based on the total weight of the composition, calculated as SiC>2.

[0034] In a further aspect, the composition according to the present invention comprises zirconium ions, rare earth ions such as lanthanum and cerium, niob ions and phosphate ions, tin ions, strontium ions, antimony ions and sulfur ions in an amount of 0 to 6 wt.%, preferably 0 to 4 wt.%, more preferably 0 to 3 wt.%, based on the total weight of the composition, calculated as ZrO2, La2O3, CeO2, Nb2O5, P2O5, SnO2 / SnO, SrO, Sb2O3, Sb2S3or SO3.

[0035] The present composition can be provided and used for the intended purpose in two different embodiments.

[0036] First embodiment

[0037] In the first embodiment of the present invention, the above-mentioned glass composition is supplemented with iron ions and manganese ions and thereafter molted. The resulting molted glass frit, is then used for the intended purpose of digesting commercially available low-E coating systems and to fuses directly to the glass surface (bare glass) providing thereby the proper anti-stick properties necessary for press bending.

[0038] In this first embodiment, the composition according to the present invention further comprises preferably 0,1 to 7 wt.%, more preferably 0,1 to 5 wt.%, even more preferably 0,1 to 3 wt.%, iron ions, based on the total weight of the composition, calculated as Fe2O3.

[0039] In this first embodiment, the composition according to the present invention further comprises preferably 0,1 to 7 wt.%, more preferably 0,1 to 5 wt.%, even more preferably 0 to 3 wt.%, manganese ions, based on the total weight of the composition, calculated as MnO.

[0040] In this first embodiment, the composition according to the present invention further comprises preferably 0,1 to 7 wt.% iron ions, based on the total weight of the composition, calculated as Fe2C>3, and preferably 0,1 to 7 wt.%, more preferably 0,1 to 5 wt.%, even more preferably 0 to 3 wt.%, manganese ions, based on the total weight of the composition, calculated as MnO. In this first embodiment, the composition according to the present invention further comprises preferably 0,1 to 5 wt.% iron ions, based on the total weight of the composition, calculated as Fe2C>3, and preferably 0,1 to 7 wt.%, preferably 0,1 to 5 wt.%, more preferably 0 to 3 wt.%, manganese ions, based on the total weight of the composition, calculated as MnO.

[0041] In this first embodiment, the composition according to the present invention further comprises preferably 0,1 to 3 wt.% iron ions, based on the total weight of the composition, calculated as Fe2C>3, and preferably 0,1 to 7 wt.%, preferably 0,1 to 5 wt.%, more preferably 0 to 3 wt.%, manganese ions, based on the total weight of the composition, calculated as MnO.

[0042] In this first embodiment, the composition according to the present invention is free of Al2O3. Based on the above-mentioned components of the composition according to the present invention, the resulting composition has a softening point below 480 °C, preferably below 465 °C, more preferably below 450 °C and liquidus temperature below 650°C. which provides a dissolving at lower temperatures and gives a better fit with firing condition for automotive application.

[0043] In the first embodiment of the present invention, the composition according to the present invention is molten and used for the intended purpose in the form of molten glass.

[0044] In the following, further aspects of the first embodiments are described.

[0045] The composition according to the first composition comprises a glass composition, comprising, based on the total weight of the composition,

[0046] bismuth ions calculated as Bi2O3in an amount of 30 to 80 wt.%,

[0047] zinc ions calculated as ZnO in an amount of 3 to 30 wt.%,

[0048] boron ions calculated as B2O3 in an amount of 0,1 to 20 wt.%,

[0049] alkali ions such as sodium ions, potassium ions and lithium ions.% calculated as Na2O, K2O, and Li2O. in an amount of 0,1 to 10 wt. %, preferably 0,1 to 8 wt.-%, more preferably 0,1 to 7 wt.-%,

[0050] whereby the glass composition further comprises preferably 0,1 to 7 wt.%, more preferably 0,1 to 5 wt.%, more preferably 0,1 to 3 wt.%, iron ions, based on the total weight of the composition, each calculated as Fe2Os, and

[0051] wherein the weight ratio between bismuth ions and zinc ions, calculated as Bi2O3and ZnO, is 3 to 14.

[0052] The composition according to the first composition comprises a glass composition, comprising, based on the total weight of the composition,

[0053] bismuth ions calculated as Bi2O3in an amount of 30 to 80 wt.%, zinc ions calculated as ZnO in an amount of 3 to 30 wt.%,

[0054] boron ions calculated as B2O3 in an amount of 0,1 to 20 wt.%,

[0055] alkali ions such as sodium ions, potassium ions and lithium ions.% calculated as Na2O, K2O, and Li2O. in an amount of 0,1 to 10 wt.-%, preferably 0,1 to 8 wt.-%, more preferably 0,1 to 7 wt.-%,

[0056] whereby the glass composition further comprises preferably 0,1 to 7 wt.%, more preferably 0,1 to 5 wt.%, more preferably 0 to 3 wt.%, manganese ions, based on the total weight of the composition, each calculated as MnO, and

[0057] wherein the weight ratio between bismuth ions and zinc ions, calculated as Bi2O3and ZnO, is 3 to 14.

[0058] The composition according to the first composition comprises a glass composition, comprising, based on the total weight of the composition,

[0059] bismuth ions calculated as Bi2O3in an amount of 30 to 80 wt.%,

[0060] zinc ions calculated as ZnO in an amount of 3 to 30 wt.%,

[0061] boron ions calculated as B2O3 in an amount of 0,1 to 20 wt.%,

[0062] alkali ions such as sodium ions, potassium ions and lithium ions.% calculated as Na2O, K2O, and Li2O. in an amount of 0,1 to 10 wt.%, %, preferably 0,1 to 8 wt%, more preferably 0,1 to 7 wt%,

[0063] iron ions in an amount of preferably 0,1 to 7 wt.%, more preferably 0,1 to 5 wt.%, more preferably 0,1 to 3 wt.%, based on the total weight of the composition, each calculated as Fe2O3,

[0064] manganese ions in an amount of preferably 0,1 to 7 wt.%, more preferably 0,1 to 5 wt.%, more preferably 0,1 to 3 wt.%, based on the total weight of the composition, each calculated as MnO,

[0065] wherein the weight ratio between bismuth ions and zinc ions, calculated as Bi2O3and ZnO, is 3 to 14.

[0066] The composition according to the first composition comprises a glass composition, comprising, based on the total weight of the composition,

[0067] bismuth ions calculated as Bi2Os in an amount of 40 to 79 wt.%,

[0068] zinc ions calculated as ZnO in an amount of 3 to 20 wt.%,

[0069] boron ions calculated as B2Osin an amount of 0,1 to 18 wt.%, alkali ions such as sodium ions, potassium ions and lithium ions.% calculated as Na2O, K2O, and Li2O. in an amount of 0,1 to 8 wt.%,

[0070] whereby the glass composition further comprises preferably 0,1 to 7 wt.%, more preferably 0,1 to 5 wt.%, more preferably 0,1 to 3 wt.%, iron ions, based on the total weight of the composition, each calculated as Fe2Oa, and

[0071] wherein the weight ratio between bismuth ions and zinc ions, calculated as Bi20a and ZnO, is 5 to 14.

[0072] The composition according to the first composition comprises a glass composition, comprising, based on the total weight of the composition,

[0073] bismuth ions calculated as E Os in an amount of 40 to 79 wt.%,

[0074] zinc ions calculated as ZnO in an amount of 3 to 20 wt.%,

[0075] boron ions calculated as E^Osin an amount of 0,1 to 18 wt.%,

[0076] alkali ions such as sodium ions, potassium ions and lithium ions.% calculated as Na2O, K2O, and Li2O. in an amount of 0,1 to 8 wt.%,

[0077] whereby the glass composition further comprises preferably 0,1 to 7 wt.%, more preferably 0,1 to 5 wt.%, more preferably 0 to 3 wt.%, manganese ions, based on the total weight of the composition, each calculated as MnO, and

[0078] wherein the weight ratio between bismuth ions and zinc ions, calculated as Bi20a and ZnO, is 5 to 14.

[0079] The composition according to the first composition comprises a glass composition, comprising, based on the total weight of the composition,

[0080] bismuth ions calculated as Bi2O3in an amount of 40 to 79 wt.%,

[0081] zinc ions calculated as ZnO in an amount of 3 to 20 wt.%,

[0082] boron ions calculated as B2Osin an amount of 0,1 to 18 wt.%,

[0083] alkali ions such as sodium ions, potassium ions and lithium ions.% calculated as Na2O, K2O, and Li2O. in an amount of 0,1 to 8 wt.%,

[0084] whereby the glass composition further comprises preferably 0,1 to 7 wt.%, more preferably 0,1 to 5 wt.%, more preferably 0,1 to 3 wt.%, iron ions, based on the total weight of the composition, calculated as Fe2Oa, and

[0085] whereby the glass composition further comprises preferably 0,1 to 7 wt.%, more preferably 0,1 to 5 wt.%, more preferably 0 to 3 wt.%, manganese ions, based on the total weight of the composition, each calculated as MnO, and wherein the weight ratio between bismuth ions and zinc ions, calculated as Bi20a and ZnO, is 5 to 14.

[0086] The composition according to the first composition comprises a glass composition, comprising, based on the total weight of the composition,

[0087] bismuth ions calculated as E Osin an amount of 60 to 78 wt.%,

[0088] zinc ions calculated as ZnO in an amount of 5 to 18 wt.%,

[0089] boron ions calculated as E^Osin an amount of 0,1 to 15 wt.%,

[0090] alkali ions such as sodium ions, potassium ions and lithium ions.% calculated as Na2O, K2O, and Li2O. in an amount of 0,1 to 7 wt.%,

[0091] whereby the glass composition further comprises preferably 0,1 to 7 wt.%, more preferably 0,1 to 5 wt.%, more preferably 0,1 to 3 wt.%, iron ions, based on the total weight of the composition, each calculated as Fe2Oa, and

[0092] wherein the weight ratio between bismuth ions and zinc ions, calculated as Bi2Oa and ZnO, is 7 to 14.

[0093] The composition according to the first composition comprises a glass composition, comprising, based on the total weight of the composition,

[0094] bismuth ions calculated as Bi2O3in an amount of 60 to 78 wt.%,,

[0095] zinc ions calculated as ZnO in an amount of 5 to 18 wt.%,

[0096] boron ions calculated as B2Osin an amount of 0,1 to 15 wt.%,

[0097] alkali ions such as sodium ions, potassium ions and lithium ions.% calculated as Na2O, K2O, and Li2O. in an amount of 0,1 to 7 wt.%,

[0098] whereby the glass composition further comprises preferably 0,1 to 7 wt.%, more preferably 0,1 to 5 wt.%, more preferably 0 to 3 wt.%, manganese ions, based on the total weight of the composition, each calculated as MnO, and

[0099] wherein the weight ratio between bismuth ions and zinc ions, calculated as Bi20a and ZnO, is 7 to 14.

[0100] The composition according to the first composition comprises a glass composition, comprising, based on the total weight of the composition,

[0101] bismuth ions calculated as Bi2O3in an amount of 60 to 78 wt.%,

[0102] zinc ions calculated as ZnO in an amount of 5 to 18 wt.%, boron ions calculated as B2O3 in an amount of 0,1 to 15 wt.%,

[0103] alkali ions such as sodium ions, potassium ions and lithium ions.% calculated as Na2O, K2O, and Li2O. in an amount of 0,1 to 7 wt.%,

[0104] whereby the glass composition further comprises preferably 0,1 to 7 wt.%, more preferably 0,1 to 5 wt.%, more preferably 0,1 to 3 wt.%, iron ions, based on the total weight of the composition, each calculated as Fe2Oa, and

[0105] whereby the glass composition further comprises preferably 0,1 to 7 wt.%, more preferably 0,1 to 5 wt.%, more preferably 0 to 3 wt.%, manganese ions, based on the total weight of the composition, each calculated as MnO, and

[0106] wherein the weight ratio between bismuth ions and zinc ions, calculated as Bi2O3and ZnO, is 7 to 14.

[0107] The alkali oxides are preferred to reduce the softening point of the claimed composition, but it is also possible to achieve a proper composition without alkali oxides.

[0108] In a further aspect, the above-mentioned compositions according to the present invention comprises silicon ions in an amount of 0 to 5 wt.%, preferably 0 to 3 wt.%, more preferably 0 to 2 wt.%, based on the total weight of the composition, calculated as SiC>2.

[0109] In a further aspect, the composition according to the present invention comprises zirconium ions, rare earth ions such as lanthanum and cerium, niob ions, tin ions and phosphate ions in an amount of 0 to 6 wt.%, preferably 0 to 4 wt.%, more preferably 0 to 3 wt.%, based on the total weight of the composition, calculated as ZrC>2, La2Os, CeC>2, Nb20s, P2O5, SnC>2 and SnO.

[0110] Second embodiment

[0111] In the second embodiment of the present invention, the above-mentioned glass composition is supplemented with black pigments containing iron in any oxidation states, with iron content of more than 30 wt% based on the total weight of the pigment composition, calculated as Fe2C>3, and / or containing manganese in any oxidation states with a manganese content of more than 30 wt%, based on the total weight of the pigment composition, calculated as MnO. In this second embodiment, the iron containing pigment is selected from the group, consisting of Fe, FexSi1-x(x = 0,01 - 1), FesO4, FeOOH, ZnFe2O4, (Cr. Fe^Ch, Fe2Os, MnFe2O4, (Fe, Cr)2O4, (Co, Fe)(Fe, Cr)2O4, (Ni, Fe)(Cr, Fe)2O4, Fe2TiO4, Fe2TiOs, MnFe2O4, FeS and mixtures thereof. The iron containing pigment comprises iron preferably in an oxidation state +2 or +3.

[0112] In this second embodiment, the manganese containing pigment is preferably selected from the group consisting of manganese ferrite, bismuth manganese oxide, bixbyite, MnC>2, M^Ch and Mn3C>4. In the second embodiment, the above-mentioned glass composition is supplemented with preferably 0,1 to 25 wt.%, more preferably 0,1 to 22 wt.%, based on the total weight of the composition, of a high iron containing black pigment.

[0113] In the second embodiment, the above-mentioned glass composition is supplemented with preferably 0,1 to 10 wt.%, more preferably 0,1 to 6 wt.%, more preferably 0,1 to 4 wt.%, based on the total weight of the composition, of a high manganese containing black pigment.

[0114] In the second embodiment of the present invention, the composition according to the present invention is provided by a physical mixture of the above-mentioned glass composition and the additional supplements of the high iron-containing pigment and the high manganese-contain-ing pigment, and other frits, pigments and fillers. The composition of the second embodiment is used as a physical mixture for the intended purpose.

[0115] In the following, further aspects of the first embodiments are described.

[0116] The composition according to the second composition comprises a glass composition, comprising, based on the total weight of the composition,

[0117] bismuth ions in an amount of 30 to 80 wt.%, calculated as E Os,

[0118] zinc ions in an amount of 3 to 30 wt.%, calculated as ZnO,

[0119] boron ions in an amount of 0,1 to 20 wt.%, calculated as B2O3,

[0120] alkali ions such as sodium ions, potassium ions and lithium ions.% calculated as Na2O, K2O, and Li2O. in an amount of 0,1 to 10 wt.%, preferably 0,1 to 8 wt.%, more preferably 0,1 to 7 wt.%,

[0121] whereby the glass composition is provided in a physical mixture with a high iron containing pigment in an amount of preferably 0,1 to 30 wt.%, preferably 0,1 to 25 wt.%, more preferably 0,1 to 22 wt.%, based on the total weight of the composition, and

[0122] wherein the weight ratio between bismuth ions and zinc ions, calculated as Bi2Os and ZnO, in the glass composition is 3 to 14.

[0123] The composition according to the second composition comprises a glass composition, comprising, based on the total weight of the composition,

[0124] bismuth ions in an amount of 30 to 80 wt.%, calculated as Bi2O3,

[0125] zinc ions in an amount of 3 to 30 wt.%, calculated as ZnO,

[0126] boron ions in an amount of 0,1 to 20 wt.%, calculated as B2O3,

[0127] alkali ions such as sodium ions, potassium ions and lithium ions.% calculated as Na2O, K2O, and Li2O. in an amount of 0,1 to 10 wt.%, preferably 0,1 to 8 wt. %, more preferably 0,1 to 7 wt.%, whereby the glass composition is provided in a physical mixture with a high manganese containing pigment in an amount of preferably 0,1 to 10 wt.%, more preferably 0,1 to 6 wt.%, more preferably 0,1 to 4 wt.%, based on the total weight of the composition, and

[0128] wherein the weight ratio between bismuth ions and zinc ions, calculated as Bi2Os and ZnO, in the glass composition is 3 to 14.

[0129] The composition according to the second composition comprises a glass composition, comprising, based on the total weight of the composition,

[0130] bismuth ions in an amount of 30 to 80 wt.%, calculated as E Os,

[0131] zinc ions in an amount of 3 to 30 wt.%, calculated as ZnO,

[0132] boron ions in an amount of 0,1 to 20 wt.%, calculated as B2O3,

[0133] alkali ions such as sodium ions, potassium ions and lithium ions.% calculated as Na2O, K2O, and Li2O. in an amount of 0,1- 10 wt. %

[0134] whereby the glass composition is provided in a physical mixture with a high iron containing pigment in an amount of preferably 0,1 to 30 wt.%, preferably 0,1 to 25 wt.%, more preferably 0,1 to 22 wt.%, based on the total weight of the composition,

[0135] whereby the glass composition is provided in a physical mixture with a high manganese containing pigment in an amount of preferably 0,1 to 10 wt.%, more preferably 0,1 to 6 wt.%, more preferably 0,1 to 4 wt.%, based on the total weight of the composition, and

[0136] wherein the weight ratio between bismuth ions and zinc ions, calculated as Bi2Oa and ZnO, in the glass composition is 3 to 14.

[0137] The composition according to the second composition comprises a glass composition, comprising, based on the total weight of the composition,

[0138] bismuth ions in an amount of 40 to 75 wt.%, calculated as Bi2Os,

[0139] zinc ions in an amount of 3 to 20 wt.%, calculated as ZnO,

[0140] boron ions in an amount of 0,1 to 18 wt.%, calculated as B2O3,

[0141] alkali ions such as sodium ions, potassium ions and lithium ions.% calculated as Na2O, K2O, and Li2O. in an amount of 0,1- 8 wt. %

[0142] whereby the glass composition is provided in a physical mixture with a high iron containing pigment in an amount of preferably 0,1 to 30 wt.%, preferably 0,1 to 25 wt.%, more preferably 0,1 to 22 wt.%, based on the total weight of the composition, and

[0143] wherein the weight ratio between bismuth ions and zinc ions, calculated as Bi2Os and ZnO, in the glass composition is 5 to 14. The composition according to the second composition comprises a glass composition, comprising, based on the total weight of the composition,

[0144] bismuth ions in an amount of 40 to 75 wt.%, calculated as E Os,

[0145] zinc ions in an amount of 3 to 20 wt.%, calculated as ZnO,

[0146] boron ions in an amount of 0,1 to 18 wt.%, calculated as B2O3,

[0147] alkali ions such as sodium ions, potassium ions and lithium ions.% calculated as Na2O, K2O, and Li2O. in an amount of 0,1 to 8 wt.%, preferably 0,1 to 7 wt.%,

[0148] whereby the glass composition is provided in a physical mixture with a high manganese containing pigment in an amount of preferably 0,1 to 10 wt.%, more preferably 0,1 to 6 wt.%, more preferably 0,1 to 4 wt.%, based on the total weight of the composition, and

[0149] wherein the weight ratio between bismuth ions and zinc ions, calculated as Bi2Os and ZnO, in the glass composition is 5 to 14.

[0150] The composition according to the second composition comprises a glass composition, comprising, based on the total weight of the composition,

[0151] bismuth ions in an amount of 40 to 79 wt.%, calculated as Bi2O3,

[0152] zinc ions in an amount of 3 to 20 wt.%, calculated as ZnO,

[0153] boron ions in an amount of 0,1 to 18 wt.%, calculated as B2O3,

[0154] alkali ions such as sodium ions, potassium ions and lithium ions.% calculated as Na2O, K2O, and Li2O. in an amount of 0,1 to 8 wt.%, preferably 0,1 to 7 wt.%,

[0155] whereby the glass composition is provided in a physical mixture with a high iron containing pigment in an amount of preferably 0,1 to 30 wt.%, preferably 0,1 to 25 wt.%, more preferably 0,1 to 22 wt.%, based on the total weight of the composition

[0156] whereby the glass composition is provided in a physical mixture with a high manganese containing pigment in an amount of preferably 0,1 to 10 wt.%, more preferably 0,1 to 6 wt.%, more preferably 0,1 to 4 wt.%, based on the total weight of the composition, and

[0157] wherein the weight ratio between bismuth ions and zinc ions, calculated as Bi2Os and ZnO, in the glass composition is 5 to 14.

[0158] The composition according to the second composition comprises a glass composition, comprising, based on the total weight of the composition,

[0159] bismuth ions in an amount of 60 to 78 wt.%, calculated as Bi2Os,

[0160] zinc ions in an amount of 5 to 18wt.%, calculated as ZnO, boron ions in an amount of 0,1 to 15 wt.%, calculated as B2O3,

[0161] alkali ions such as sodium ions, potassium ions and lithium ions.% calculated as Na2O, K2O, and Li2O. in an amount of 0,1 to 7 wt.%,

[0162] whereby the glass composition is provided in a physical mixture with a high iron containing pigment in an amount of preferably 0,1 to 30 wt.%, preferably 0,1 to 25 wt.%, more preferably 0,1 to 22 wt.%, based on the total weight of the composition, and

[0163] wherein the weight ratio between bismuth ions and zinc ions, calculated as Bi2Os and ZnO, in the glass composition is 7 to 14.

[0164] The composition according to the second composition comprises a glass composition, comprising, based on the total weight of the composition,

[0165] bismuth ions in an amount of 60 to 78 wt.%, calculated as Bi2O3,

[0166] zinc ions in an amount of 5 to 18 wt.%, calculated as ZnO,

[0167] boron ions in an amount of 0,1 to 15 wt.%, calculated as B2O3,

[0168] alkali ions such as sodium ions, potassium ions and lithium ions.% calculated as Na2O, K2O, and Li2O. in an amount of 0,1 to 7 wt.%,

[0169] whereby the glass composition is provided in a physical mixture with a high manganese containing pigment in an amount of preferably 0,1 to 10 wt.%, more preferably 0,1 to 6 wt.%, more preferably 0,1 to 4 wt.%, based on the total weight of the composition, and

[0170] wherein the weight ratio between bismuth ions and zinc ions, calculated as Bi2Os and ZnO, in the glass composition is 7 to 14.

[0171] The composition according to the second composition comprises a glass composition, comprising, based on the total weight of the composition,

[0172] bismuth ions in an amount of 60 to 78 wt.%, calculated as Bi2O3,

[0173] zinc ions in an amount of 5 to 18wt.%, calculated as ZnO,

[0174] boron ions in an amount of 0,1 to 15 wt.%, calculated as B2O3,

[0175] alkali ions such as sodium ions, potassium ions and lithium ions.% calculated as Na2O, K2O, and Li2O. in an amount of 0,1 to 7 wt.%,

[0176] whereby the glass composition is provided in a physical mixture with a high iron containing pigment in an amount of preferably 0,1 to 30 wt.%, preferably 0,1 to 25 wt.%, more preferably 0,1 to 22 wt.%,, based on the total weight of the composition whereby the glass composition is provided in a physical mixture with a high manganese containing pigment in an amount of preferably 0,1 to 10 wt.%, more preferably 0,1 to 6 wt.%, more preferably 0,1 to 4 wt.%, based on the total weight of the composition, and

[0177] wherein the weight ratio between bismuth ions and zinc ions, calculated as Bi2Oa and ZnO, in the glass composition is 7 to 14.

[0178] First and second embodiments

[0179] The compositions according to the first and second embodiments of the present invention may comprise up to 15 wt.% solids of a filler, selected from the group consisting of silica, alumina, zinc silicate, bismuth silicate, zinc oxide, zinc and mixtures thereof.

[0180] The compositions according to the first and second embodiments of the present invention may have preferably a D90 particle size of the solid component 0,2 to 40 pm, more preferably 0,5 to 30 pm, more preferably 0,7 to 20 pm, whereby the D90 particle size is measured by laser diffraction according to ISO 2019:13320.

[0181] The compositions according to the first and second embodiments of the present invention may have a firing temperature of preferably more than 615 °C, more preferably more than 625 °C, more preferably more than 635 °C.

[0182] The compositions according to the first and second embodiments of the present invention are suitable to completely dissolve conductive metal layers, including silver, and protective ox-ide / non-oxide non-conductive layers employed in the design of Low-e coatings for automotive or architectural applications.

[0183] The compositions according to the first and second embodiments of the present invention may be devoid of lead, cadmium, and vanadium.

[0184] The compositions according to the first and second embodiments of the present invention may further comprise at least one crystallizing agent.

[0185] The compositions according to the first and second embodiments of the present invention may further comprise black pigments, such as as Cu-Cr spinels and / or Mn-Cu-Cr spinels.

[0186] The compositions according to the first and second embodiments of the present invention may further comprise an organic vehicle suitable for screen printing, inkjet printing, roller coating and spray coating.

[0187] The present invention further relates to a method of preparing the compositions according to the first or second embodiment of the present invention.

[0188] For this purpose, at first the glass frit which is common in the compositions according to the first and second embodiment are prepared and then ground to a fine powder using conventional methods. The frit component is then combined with the other solids components accord- ing to the first and second embodiment. Thereby, the composition according to the first embodiment is molten whereas the composition according to the second embodiment is physically mixed with the other solids components. The resulting mixtures are then mixed with a vehicle to form the enamel paste or ink.

[0189] The viscosity may be adjusted as desired for the specific application purpose.

[0190] Once the enamel paste is prepared, it can be applied to the substrate in a conventional manner such as by screen printing, roller coating, inkjet printing or the like.

[0191] Thereby, wet film thickness is preferably between 8 and 50 pm, in particular between 10 and 40 pm.

[0192] Therefore, a further subject-matter of the present invention is a method of applying the composition according to the first and second embodiments of the present invention by using screen printing, inkjet printing, roller coating and spray coating.

[0193] In the claimed method, the application of the composition according to the first and second embodiments of the present invention is carried out on a Low-e coated side of a glass surface. In the claimed method, the glass surface is preferably a surface of a soda-lime glass, borosilicate, aluminosilicate glasses and / or lion glass.

[0194] Lion glass is a phosphate-rich, carbonate-free family of glasses having the following typical composition window (mol%):

[0195] . P2O5: -25-55

[0196] • SiO2: -5-45

[0197] . AI2O3: -5-22

[0198] . ZnO: -5-30

[0199] . Na2O / K2O / Li2O (sum): >0-20

[0200] • CaO and / or MgO: -2-8 each

[0201] These batches are melted at roughly 1000 to 1300 °C, notably lower than soda-lime, and avoid carbonate raw materials (soda ash / limestone), which helps cut CO2emissions.

[0202] In the claimed method, the composition according to the first and second embodiments of the present invention preferably dissolve conductive metal layers, including silver, and protective oxide / non-oxide non-conductive layers employed in the design of Low-e coatings for automotive or architectural applications. After application of the paste or ink to a coated substrate in a desired pattern, the applied enamel is then fired to dissolve the Low E-coating and bond the enamel to the glass substrate and forms a non sticking surface which is required for the bending.

[0203] The bending of the enameled glass sheet can be done by gravity or press bending. This can be done in a single firing or pre-firing and a subsequent pair bending process. For the bending process a separation powder is additionally used.

[0204] In the pre-firing step the coating is completely or partially dissolved and is then completely dissolved during a second bending firing. The firing range is typically in the range of about 570 to 750 ° C, more preferably in the range of about 615 to 700 °C.

[0205] The desired firing range can be adjusted by the content of composition.

[0206] Finally, the present invention also relates to the use of a composition according to the first and second embodiments of the present invention for press-bending used in automotive glass manufacturing.

[0207] To summarize the present invention, the present invention focusses in particular on a non-stick glass enamel formulated for the dissolution of low emissivity (low-e) coatings comprising at least one infrared (IR) reflecting layer sandwiched between dielectric layers applied on glass surfaces, designed for use in both automotive and architectural applications, wherein either glass phase (frit) or filler / pigment or both may contain iron and manganese in any oxidation state. In this preferred embodiment a composition, comprising, based on the total weight of the composition, bismuth ions in an amount of 30 to 80 wt. %, calculated as Bi2Os, zinc ions in an amount of 3 to 30 wt. %, calculated as ZnO, boron ions in an amount of 0,1 to 20 wt. %, calculated as B2O3, alkali ions such as sodium ions, potassium ions and lithium ions in an amount of 0,1 to 10 wt.%, calculated as Na2O, K2O, and Li2O. characterized in that the weight ratio between bismuth ions and zinc ions, calculated as Bi2O3and ZnO, is 3 to 14.

[0208] To further summarize the present invention, the present invention refers to a composition applied on a Low-E coated glass substrate, which

[0209] (i) dissolves the Low-E coating during firing

[0210] (ii) forms a matt or semi matt surface

[0211] (iii) can be fired even at low temperatures of around 620 °C

[0212] (iv) comprises either glass phase (frit) or filller / pigment or both may contain iron and manganese in any oxidation state. In this embodiment a composition, comprising, based on the total weight of the composition, bismuth ions in an amount of 30-80 wt. %, calculated as Bi2Oa, zinc ions in an amount of 3 to 30 wt. %, calculated as ZnO, boron ions in an amount of 0,1 to 20 wt. %, calculated as B2O3, alkali ions such as sodium ions, potassium ions and lithium ions in an amount of 0,1 to 10 wt.%, calculated as Na2O, K2O, and Li2O characteriszed in that the weight ratio between bismuth ions and zinc ions, calculated as Bi2O3and ZnO, is 3 to 14. The present invention differs from the disclosure of US 10745317 B and US 5252521 A with regard to the content of Na2O which - according to the present invention - is at least 0,1 wt.-%, whereas Na2O is not present in the prior art.

[0213] The present invention differs from the disclosure of WO 2021 / 023965 A with regard to the content of Bi2Oa which is at most 80 wt.-% in the present invention, whereas Bi2Oa is present in a higher amount in the prior art.

[0214] The present invention differs from the disclosure of WO 2021 / 107707 A by the fact that the present invention defined that the composition is free of AI2O3, whereas in the prior art at least 0,1 wt.-% AI2O3 is required.

[0215] The frit compositions according to the present invention were prepared by mixing together the required raw materials and melting them to form a molten glass melt, then quenching to form a glass frit. In the following examples different amounts of iron oxide and even manganese oxide have been added to the frit formulation.

[0216] The milled frits were mixed with pigment, fillers and organic vehicle.

[0217] The black enamel pastes have been screen printed on a triple silver coated glass and fired at different temperatures.

[0218] In following examples, the effect of iron containing pigments on the gloss reduction in the black enamel will be demonstrated.

[0219] Following are black automotive enamel formulations, made with the coating dissolving glass composition and different pigments. Table 1

[0220]

[0221] Pigment 1 is (Mn / Cu)-Cr-spinell

[0222] Pigment 2 is high Mn-containing pigment

[0223] Pigment 3 is high Fe-containing pigment

[0224] The presence of high iron or manganese containing pigments may help to reduce the gloss level of the fired black enamel while achieving good L*values and high optical densities. Even low contents of such pigment can reduce the gloss significantly.

[0225] Figure 1 shows that the gloss level of the fired enamel could be significantly reduced with increasing amounts of iron oxide. The addition of 1% manganese oxide can enhance this ef-feet.

[0226] Figure 2 the colour being measured from the glass side to check the dissolving effect of the black enamel on the Low-E coating. L*-values were measured with X-rite colorimeter.

[0227] L*-value increases with increasing amounts of iron oxide. At low temperature the coating is not completely dissolved. At higher temperatures the dissolving could be improved. As demonstrated by these examples the frit composition which contains iron and manganese can reduce the gloss level and may help achieving anti-stick enamels.

[0228] Figure 3 shows the melting behavior (heating microscope from Hesse Instruments) of the following two frits:

[0229]

Claims

Claims1. A composition, comprising, based on the total weight of the composition, bismuth ions in an amount of 30 to 80 wt.%, calculated as Bi2O3, zinc ions in an amount of 3 to 30 wt.%, calculated as ZnO, boron ions in an amount of 0,1 to 20 wt.%, calculated as B2O3, alkali ions such as sodium ions, potassium ions and lithium ions in an amount of 0,1 to 10 wt. %, calculated as Na2O, K2O, and Li2O. characterized in that the weight ratio between bismuth ions and zinc ions, calculated as Bi2O3and ZnO, is 3 to 14.

2. The composition according to claim 1, characterized in that the composition comprises bismuth ions in an amount of 40 to 79 wt%, more preferably 60 to 78 wt%, based on the total weight of the composition, calculated as Bi2O3.

3. The composition according to claim 1 or 2, characterized in that the composition comprises boron ions in an amount of 0,1 to 18 wt%, more preferably 0,1 to 15 wt%, based on the total weight of the composition, calculated as B2O3.

4. The composition according to claim 1 or 3, characterized in that the composition comprises 3 to 20 wt%, more preferably 5 to 18 wt%, zinc ions, based on the total weight of the composition, calculated as ZnO.

5. The composition according to anyone of claims 1 to 4, characterized in that the composition comprises alkali ions such as sodium ions, potassium ions and lithium ions in an amount of 0,1 to 8 wt.%, more preferably 0,1 to 7 wt.%, %, based on the total weight of the composition, sodium ions, potassium ions and lithium ions, calculated as Na2O, K2O, and Li2O.

6. The composition according to anyone of claims 1 to 5, characterized in that the composition further comprises silicon ions in an amount of 0 to 5 wt.%, preferably 0 to 3 wt.%, more preferably 0 to 2 wt.%, based on the total weight of the composition, calculated as SiO2.

7. The composition according to anyone of claims 1 to 6, characterized in that the composition further comprises 0,1 to 7 wt.%, preferably 0,1 to 5 wt.%, more preferably 0,1 to 3 wt.% iron ions, based on the total weight of the composition, calculated as Fe2O3.

8. The composition according to anyone of claims 1 to 7, characterized in that the composition further comprises zirconium ions, rare earth ions such as lanthanum and cerium, niob ions and phosphate ions, tin ions strontium, antimony ions and sulfur ions in an amount of 0 to 6 wt.%, preferably 0 to 4 wt.%, more preferably 0 to 3 wt.%, based on the total weight of the composition, calculated as ZrC>2, La2Os, CeC>2, Nb20s, P2Os, SnCh / SnO, SrO, Sb2O3 and SO3.

9. The composition according to anyone of claims 1 to 8, characterized in that the composition further comprises 0,1 to 7 wt.%, preferably 0,1 to 5 wt.%, more preferably 0 to 3 wt.% manganese ions, based on the total weight of the composition, calculated as MnO.

10. The composition according to anyone of claim 1 to 9, characterized in that the composition is free of Al2O3.

11. The composition according to anyone of claims 1 to 10, characterized in that the composition is in the form of a molten glass.

12. The composition according to anyone of claims 1 to 11, characterized in that the composition further comprises black pigments containing iron in any oxidation states, with iron content of more than 30 wt% based on the total weight of the pigment composition, calculated as Fe2C>3, and / or containing manganese in any oxidation states, with manganese content of more than 30 wt% based on the total weight of the pigment composition, calculated as MnO.

13. The composition according to anyone of claims 1 to 7 and 12, characterized in that the composition further comprises 0,1 to 25 wt.%, preferably 0,1 to 22 wt.%, based on the total weight of the composition, of a iron containing pigment.

14. The composition according to anyone of claims 1 to 7 and 12, characterized in that the composition further comprises 0,1 to 10 wt.%, preferably 0,1 to 6 wt.%, more preferably 0,1 to 4 wt.%, based on the total weight of the composition, of a manganese containing pigment.

15. Enamel, prepared by mixing the composition according to anyone of claims 1 to 14.

16. A method of applying the composition according to anyone of claims 1 to 14, characterized in that the application is carried out using screen printing, inkjet printing, roller coating and spray coating on a low-e coated side of a glass surface.

17. The method according to claim 16, characterized in that the glass surface is a surface of a soda-lime glass, borosilicate, aluminosilicate glasses and / or lion glass.

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